CN110117281A - Organic compound and electric driven color-changing part - Google Patents

Organic compound and electric driven color-changing part Download PDF

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Publication number
CN110117281A
CN110117281A CN201910107431.0A CN201910107431A CN110117281A CN 110117281 A CN110117281 A CN 110117281A CN 201910107431 A CN201910107431 A CN 201910107431A CN 110117281 A CN110117281 A CN 110117281A
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China
Prior art keywords
electric driven
driven color
compound
changing part
organic compound
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CN201910107431.0A
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Inventor
井川悟史
山田宪司
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Canon Inc
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Canon Inc
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Priority claimed from JP2019004490A external-priority patent/JP7166939B2/en
Application filed by Canon Inc filed Critical Canon Inc
Publication of CN110117281A publication Critical patent/CN110117281A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
    • E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B11/00—Filters or other obturators specially adapted for photographic purposes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
    • E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
    • E06B2009/2464—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds featuring transparency control by applying voltage, e.g. LCD, electrochromic panels
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
    • E06B3/67—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light
    • E06B3/6715—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light specially adapted for increased thermal insulation or for controlled passage of light
    • E06B3/6722—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light specially adapted for increased thermal insulation or for controlled passage of light with adjustable passage of light
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
    • G02F2001/1635—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor the pixel comprises active switching elements, e.g. TFT

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Abstract

The present invention relates to organic compounds and electric driven color-changing part.The organic compound of an embodiment according to the present invention is the organic compound indicated by general formula (1).X1And X2It respectively can have the alkyl etc. of substituent group.R11~R18Respectively hydrogen atom or it can have the alkyl etc. of substituent group.R21And R22Respectively hydrogen atom or it can have the alkyl etc. of substituent group.A1 ‑And A2 ‑Separately indicate monovalent anion.

Description

Organic compound and electric driven color-changing part
Technical field
The present invention relates to organic compounds, and the electric driven color-changing part with the organic compound, optical filter and camera lens list Member, picture pick-up device (imaging apparatus) and window member.
Background technique
Electric driven color-changing part is the element of the electrochromic layer with a pair of electrodes and configuration between this pair of electrodes. By applying voltage, the amount of the adjustable light by electrochromic layer between this pair of electrodes.As wherein due to electrification Learn redox reaction cause substance optical absorption property (colour generation state or light transmittance) variation electrochromism (hereinafter, Also referred to as " EC ") material, it is known that such as inorganic material, high molecular material or organic low molecular material a variety of materials.Use these Material, EC element have been applied to Light-modulating mirror or Electronic Paper of automobile etc..These devices are utilized can be according to the selection of material And show the property of various tones.It means that the exploitation of the material with various tones can be wide when using EC element Range applications.For example, the application in full-color display etc. needs to be colored as the material of cyan, magenta and yellow.Wider Application range in application need the coloured materials of various tones.In addition, colouring steady with colour killing (achromatizing) It is qualitative or there are rooms for improvement in repeated durability when used for a long time.
Patent document 1 (international publication number WO2011/046222) is disclosed with the pyridine derivate of reducing condition coloring Organic compound simultaneously discloses the electric driven color-changing part for being colored as cyan, magenta and yellow.In addition, being applied in EC material Whens full-color display or colour filter etc., it is desirable to no matter use environment temperature, EC material is colored as identical color.Specially Sharp document 2 (Japanese Patent Application Laid-Open No. 2001-519922) discloses the electroluminescent of various purpurines (viologen) derivative Photochromic elements.
In order to by electric driven color-changing part investment actual use, according to the type of the device of application or purposes it is necessary to have The compound of various properties, and compound disclosed in patent document 1 and 2 is insufficient.
Summary of the invention
One embodiment of the invention is intended to provide a kind of organic compound, can by redox reaction come The light of the range near 500nm is absorbed to colour or colour killing, and there is high stability to duplicate redox reaction.
One embodiment of the invention provides a kind of organic compound indicated by following general formula (1).
In general formula (1), X1And X2Independently selected from by substituted or unsubstituted alkyl, substituted or unsubstituted aryl and The group of substituted or unsubstituted aralkyl composition.
R11~R18Independently selected from by hydrogen atom and substituent group at group, and by R11~R18Each substituent group indicated For any one in following: substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted virtue Base, substituted or unsubstituted heterocycle, halogen atom and cyano.
R21And R22Independently selected from by hydrogen atom and substituent group at group, and by R21And R22Each substituent group indicated For any one in following: substituted or unsubstituted alkyl, substituted or unsubstituted aryl and substituted or unsubstituted virtue Alkyl.
A1 -And A2 -Independently indicate monovalent anion.
Referring to attached drawing, from the description of following exemplary embodiment, further characteristic of the invention will become aobvious and easy See.
Detailed description of the invention
Fig. 1 is the schematic sectional view according to an example of the electric driven color-changing part of embodiment.
Fig. 2 is the signal for showing an example of the driving device for being connected to the electric driven color-changing part according to embodiment Figure.
Fig. 3 A and Fig. 3 B are the schematic diagram for showing an example of the picture pick-up device according to embodiment.
Fig. 4 A and Fig. 4 B are the schematic diagram for showing an example of the window member according to embodiment.
Fig. 5 is the colored state of the electric driven color-changing part of embodiment 3 and the ultraviolet-visible absorption spectroscopy of colour killing state.
Specific embodiment
Organic compound
The organic compound of an embodiment according to the present invention is the organic compound with electrochromism.Tool There is the organic compound of electrochromism to be properly termed as electrochromic compounds.In the present embodiment, electrochromic compounds It is properly termed as EC compound.In addition, in the present embodiment, statement " coloring " refers to that the transmitance under specific wavelength drops It is low.
The organic compound of an embodiment according to the present invention is indicated by following general formula (1).
In general formula (1), X1And X2Separately being selected from can have the alkyl of substituent group, can have substituent group Aryl and the aralkyl that can have substituent group.R11~R18Separately it is selected from hydrogen atom and substituent group.By R11~R18Table Each substituent group shown be it is following in any one: can have the alkyl of substituent group, the alkoxy that can have substituent group, It can have the aryl of substituent group, the heterocycle that can have substituent group, halogen atom and cyano.R21And R22Separately Selected from hydrogen atom and substituent group, and by R21And R22Each substituent group indicated is any one in following: can have and takes The alkyl of Dai Ji, the aryl that can have substituent group and the aralkyl that can have substituent group.A1 -And A2 -Independently earth's surface Show monovalent anion.
By X1And X2、R11~R18And R21And R22Each alkyl indicated preferably has 1~8 carbon atom, and can be with For straight-chain, branching shape or ring-type.In addition, hydrogen atom can be substituted with halogen atoms, preferably it is replaced by fluorine atoms.In addition, alkane The carbon atom for including in base can be replaced with ester group or cyano.Specifically, alkyl can be methyl, ethyl, n-propyl, isopropyl Base, normal-butyl, tert-butyl, octyl, cyclohexyl or trifluoromethyl etc..
In addition, by X1And X2The end of each alkyl indicated can have the adsorption group for being adsorbed to porous electrode (absorptive group) or its perester radical.The specific example of adsorption group or its perester radical can be carboxyl and carboxylate Base, sulfonic group and sulfonate group, phosphonic acid base and phosphonate group or trialkoxysilyl etc..In addition, in order to improve for The dissolubility of organic solvent, the end of alkyl can have such as pyridine or quinoline isoiony group.
By X1And X2And R21And R22Each aralkyl indicated can be benzyl or phenethyl etc..Aralkyl can have Substituent group specifically can have the alkyl with 1~8 carbon atom or the alkoxy with 1~8 carbon atom.Alkyl Or the hydrogen atom in alkoxy including can be substituted with halogen atoms, and be preferably replaced by fluorine atoms.In addition, when by X1And X2It indicates Aralkyl when there is alkyl or alkoxy, end can have adsorption group for being adsorbed to porous electrode or its acid Ester group, or can have for improving the deliquescent ionic group for organic solvent.Adsorption group or perester radical, With the specific example of ionic group and about by X1And X2Example listed by the alkyl of expression is identical.
By R11~R18Indicate each alkoxy preferably have 1~8 carbon atom and can for straight-chain, branching shape or It is cyclic annular.Specifically, alkoxy can be methoxyl group, ethyoxyl, isopropoxy, tert-butoxy, octyloxy, cyclohexyloxy or three Fluorine methoxyl group etc..In addition, the hydrogen atom for including in alkoxy can be substituted with halogen atoms.When being substituted with halogen atoms, halogen Plain atom is preferably fluorine atom.
By X1And X2、R11~R18And R21And R22Each aryl indicated can preferably be phenyl, xenyl, three Phenyl, fluorenyl, naphthalene, fluoranthene base, anthryl, phenanthryl, pyrenyl, aphthacene base, pentacene, triphenylene or base (perylenyl group) etc..When aryl has substituent group, substituent group can have halogen atom, have 1~8 carbon original The alkyl of son and in alkoxy with 1~8 carbon atom at least any one.The hydrogen for including in alkyl or alkoxy is former Son can be substituted with halogen atoms, and be preferably replaced by fluorine atoms.In addition, when by X1And X2The aryl of expression has alkyl or alcoxyl When base, end can have adsorption group or its perester radical for being adsorbed to porous electrode, or can have for changing Into the deliquescent ionic group for organic solvent.The specific example of adsorption group or its perester radical and ionic group With about by X1And X2Example listed by the alkyl of expression is identical.
By R11~R18Each heterocycle indicated can be thienyl, pyrrole radicals, pyridyl group, oxazolyl, oxadiazoles base, thiophene Oxazolyl, thiadiazolyl group, terthienyl, quinolyl, isoquinolyl or carbazyl etc..When heterocycle has substituent group, substituent group Can have in the alkyl with 1~8 carbon atom and the alkoxy with 1~8 carbon atom at least any one.Alkane The hydrogen atom for including in base or alkoxy can be substituted with halogen atoms, and be preferably replaced by fluorine atoms.
By R11~R18Each halogen atom indicated can be fluorine, chlorine, bromine or iodine etc..
A1 -And A2 -It can be identical or different and selected from such as PF6 -、ClO4 -、BF4 -、AsF6 -、SbF6 -、 CF3O3 -Or (CF3SO2)2N-Equal anion, or such as Br-、Cl-Or I-Equal halide anions, and can be preferably PF6 -、ClO4 -、BF4 -、 CF3SO3 -Or (CF3SO2)2N-In any one.It is highly preferred that A1 -And A2 -For identical anion.
Although the production method of the organic compound of an embodiment according to the present invention is not particularly limited, have Machine compound can for example be produced by method described below.Work as X1And X2When for alkyl and aralkyl, organic compound Can by the organic compound that is indicated by following general formula (2) and halogen compounds reacting in scheduled solvent, then with Salt comprising desired anion anion exchange reaction in the scheduled solvent obtains.Work as X1And X2It is organic when for aryl Compound can be by reacting with dinitrophenyl group halide, synthesizing dinitrophenyl group -2,7 '-diaza fluorenes (diazafluorenium), it is then reacted with arylamine, and handed over anion-containing salt anion in predetermined solvent is wrapped Reaction is changed to obtain.In addition, solvent and reaction temperature are appropriately selected such that the imine reaction of only side.It is anti-by repeating It answers, substituent group different from each other can be introduced into two imines.
Although the production method of the organic compound indicated by formula above (2) is not particularly limited, organise Closing object can for example produce according to production method described below.R in synthetic route11~R18And R21And R22With with it is logical The similar mode of formula (1) indicates that hydrogen atom or substituent group and X indicate halogen atom.
Intermediate 1 can by N, nicamide derivative and 4- it is halogenated-coupling of quinoline closes At.Intermediate 2 can be synthesized by the cyclization of the use lithium diisopropylamide (LDA) of intermediate 1.In addition, intermediate Body 3 can pass through Wolff-Kishner reduction (Wolff-Kishner reduction) Lai Hecheng of intermediate 2.By general formula (2) organic compound indicated can be synthesized by the reaction of intermediate 3 and desired halogen species in the presence of base.
The concrete structure formula of the organic compound of an embodiment according to the present invention be will be shown below as example. However, compound according to the present invention is without being limited thereto.
Due to having the structure indicated by general formula (1), thus the organic compound of an embodiment according to the present invention For when being dissolved in solvent with the compound of high transparency.In addition, an embodiment according to the present invention organises Closing object is the compound coloured with reducing condition.It is visible light under wherein reducing condition with the compound of reducing condition coloring Transmitance is lower than the compound of the transmitance of visible light under the state of oxidation.An embodiment according to the present invention organises Closing object is to show the electrochromic material of stable coloring to environment temperature and can be used for EC element and use the EC element Optical filter, lens unit and picture pick-up device etc..The organic compound of an embodiment according to the present invention is with the side The compound that formula is coloured with reducing condition can absorb the light of the range near 500nm by redox reaction, and It can colour or colour killing, and there is high stability to the repetition of redox reaction.
EC element
The EC compound of an embodiment according to the present invention may be used as the electrochromic layer of electric driven color-changing part. Description that hereinafter reference will be made to the drawings is according to the electric driven color-changing part of the present embodiment.Hereinafter, electric driven color-changing part can be expressed as EC element.
The EC element 1 of Fig. 1 is to have electricity between this pair of of transparent electrode 11 with a pair of of transparent electrode 11 and configuration Solve the EC element of the EC layer 12 of matter and EC compound according to the present invention.This pair of of transparent electrode 11 is inserted into spacer 13, thus There is certain distance between transparent electrode 11.In EC element 1, the configuration of a pair of of transparent electrode 11 a pair of of transparent substrate 10 it Between.
EC layer 12 has the EC compound of an embodiment according to the present invention.EC layer 12 can have by EC chemical combination The layer that object is constituted and the layer being made of electrolyte.In addition, EC layer 12 can be set to have the molten of EC compound and electrolyte Liquid.It is preferably the EC element that wherein EC layer 12 is solution according to the EC element of the present embodiment.
Next, description to be formed to the component of the EC element 1 according to the present embodiment.Electrolyte is not particularly limited, As long as it is ionic dissociation salt and shows to solvent good dissolubility and the high-compatibility in solid electrolyte. Particularly, electron donating property electrolyte is preferred.These electrolyte are referred to as support electrolyte matter (support electrolyte).Electrolyte for example can be such as various alkali metal salts or alkali earth metal salt inorganic ion salt, quaternary ammonium Salt or cyclic quaternary ammonium salts etc..Specifically, electrolyte can be for such as LiClO4、LiSCN、LiBF4、LiAsF6、LiCF3SO3、 LiPF6、LiI、NaI、NaSCN、 NaClO4、NaBF4、NaAsF6, the alkali metal salt of Li, Na or K such as KSCN or KCl etc., and such as (CH3)4NBF4、(C2H5)4NBF4、(n-C4H9)4NBF4、(n-C4H9)4NPF6、(C2H5)4NBr、 (C2H5)4NClO4Or (n- C4H9)4NClO4Equal quaternary ammonium salts and cyclic quaternary ammonium salts etc..
Although being not particularly limited, as long as it can dissolve EC compound or electrolyte, EC compound and electricity Solution matter, which is dissolved in solvent therein, preferably especially has polar solvent.Specifically, solvent can be water, or such as methanol, Ethyl alcohol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxy-ethane, gamma-butyrolacton, gamma-valerolactone, ring fourth Sulfone, dimethylformamide, dimethoxy-ethane, tetrahydrofuran, acetonitrile, propionitrile, benzonitrile, dimethyl acetamide, crassitude The organic polar solvents such as ketone or dioxolanes.
In addition, the material with high slumpability for further including polymer or the agent that is gelled can be used for EC layer 12 Material or material as a form of gel etc..Polymer is not particularly limited, and can be for example, polyacrylonitrile, carboxymethyl cellulose, Polyvinyl chloride, polyethylene oxide, polypropylene oxide, polyurethane, polyacrylate, polymethacrylates, polyamide, poly- third Acrylamide, polyester or Nafion (registered trademark) etc..
Next, will description transparent substrate 10 and transparent electrode 11.For transparent substrate 10, it is, for example, possible to use colourless Or coloured glass or tempered glass etc., further, it is possible to use colorless or colored transparent resin, it is noted that the art in the present embodiment " transparent " transmitance for indicating visible light of language is 90% or more.Specifically, polyethylene terephthalate can be used, gather (ethylene naphthalate), polyamide, polysulfones, polyether sulfone, polyether-ether-ketone, polyphenylene sulfide, polycarbonate, gathers polynorbornene Acid imide or polymethyl methacrylate etc..
The material of transparent electrode 11 can be for example, as tin indium oxide alloy (ITO), Fluorin doped tin oxide (FTO), Metals or the gold such as tin oxide (NESA), indium zinc oxide (IZO), silver oxide, vanadium oxide, molybdenum oxide, gold, silver, platinum, copper, indium or chromium Belong to oxide, such as polysilicon or amorphous silicon silicon systems material, or such as carbon black, graphite or vitreous carbon carbon material etc..In addition, Obtaining improved electric conductive polymer by conductivity such as doping treatments, it is preferable to use for example, polyaniline, polypyrrole gather Thiophene, polyacetylene, polyparaphenylene (polyparaphenylene) or polyethylene dioxythiophene (PEDOT) and polyphenyl second The complex etc. of alkene sulfonate (polystyrene sulfonate).
Furthermore, it is possible to which porous electrode is arranged in transparent electrode 11.Porous electrode can be preferably on surface and internal tool The material for having the surface area of porous shape, rod shape or wire shaped of micropore etc. big.The material of porous electrode can be for Such as, metal, metal oxide or carbon etc..It is highly preferred that can be used such as titanium oxide, tin oxide, ferriferous oxide, strontium oxide strontia, oxygen Change the metal oxides such as tungsten, zinc oxide, tantalum oxide, vanadium oxide, indium oxide, nickel oxide, manganese oxide or cobalt oxide.
The configuration of spacer 13 is between a pair of of transparent electrode 11 and provides with an embodiment according to the present invention The EC layer 12 of EC compound be contained in space therein.Specifically, polyimides, polytetrafluoroethylene (PTFE), fluorubber can be used Or epoxy resin etc..The spacer 13 is able to maintain the distance between transparent electrode 11 of EC element 1.
It can have the liquid injection port by a pair of electrodes and spacer formation according to the EC element 1 of the present embodiment. From liquid injection port injection have EC compound composition and sealing after, inlet by containment member cover and Further glued dose of sealing, it is hereby achieved that element.Containment member be also responsible for the isolation of bonding agent and EC compound so that It does not contact each other.Although the shape of containment member is not particularly limited, such as the shape that wedge shape is tapered (tapered shape) is preferred.
It is not particularly limited according to the forming method of the EC element 1 of the present embodiment, and can be used will be comprising pre- First pass through the liquid of the EC compounds of preparations such as vacuum impregnation, atmosphere injection method or meniscus (meniscus method) The method being infused in the gap being arranged between a pair of electrodes substrate.
It can have the organic compound of an embodiment according to the present invention according to the EC element 1 of the present embodiment With with the different types of other organic compounds (the second organic compound) of the above organic compound.It can be used a kind of or more Kind of the second organic compound, and can be used with the compound of state of oxidation coloring, with the compound of reducing condition coloring or Person has the compound of both properties.Since the organic compound of an embodiment according to the present invention is with also original state The compound of state coloring, the second organic compound are preferably the compound coloured with the state of oxidation.The change coloured with the state of oxidation Close the compound that object is lower than the transmitance of visible light under reducing condition for the transmitance of visible light under the wherein state of oxidation.
The organic compound of an embodiment according to the present invention is combined with the coloured material of other colors and can be shown As the desired color of EC element.When coloring the organic compound of other types preferably have within the scope of 400nm~800nm, Absorbing wavelength within the scope of more preferable 420nm~700nm.Refer to the peak of absorption spectrum with the absorbing wavelength in particular range It needs in particular range.By combining the organic compound and a number of other materials of an embodiment according to the present invention, The light absorbed in entire visible range and the EC element 1 for being colored as black can also be made.
It can be for example following compound according to second organic compound of the present embodiment.With state of oxidation coloring Compound can be such as 5,10- dihydro -5,10- dimethylphenazine or 5,10- dihydro -5,10- diethyl azophenlyene azophenlyene chemical combination Object, such as ferrocene, tetra-tert ferrocene or titanocenes metallocene compound, such as N, N ', N, N '-tetramethyl-para-phenylene diamine Etc. phenylenediamine compounds, or such as 1- phenyl -2- pyrrolin pyrazoline compounds etc..
It can be for such as N, two perchlorate of N'- diheptyl bipyridyl, N, N'- bis- with the compound of reducing condition coloring Two-tetrafluoroborate of heptyl bipyridyl, N, two-hexafluorophosphate of N'- diheptyl bipyridyl, N, N'- diethyl bipyridyl Two perchlorate, N, two-tetrafluoroborate of N'- diethyl bipyridyl, N, N'- diethyl two-hexafluorophosphoric acid of bipyridyl Salt, N, two perchlorate of N'- dibenzyl bipyridyl, N, two-tetrafluoroborate of N'- dibenzyl bipyridyl, N, N'- dibenzyl Two-hexafluorophosphate of base bipyridyl, N, two perchlorate of N'- diphenyl bipyridyl, N, N'- diphenyl bipyridyl two- Tetrafluoroborate or N, the viologen compounds such as N'- diphenyl two-hexafluorophosphate of bipyridyl, such as 2- ethyl hydrazine, the tertiary fourth of 2- The anthraquinone compounds such as base anthraquinone or prestox anthraquinone, such as ferrocene tetrafluoroborate or ferrocene hexafluorophosphate two Luxuriant molysite compound or compound of styryl etc..
Second organic compound is preferably arbitrary compound phenazine, metallocene compound, phenylenediamine in above compound Compound and pyrazoline compounds.
It can be confirmed by known extraction and analysis method, according to the EC layer for including in the EC element 1 of the present embodiment Compound included in 12 is included in EC element 1.For example, can using by chromatography extract, and then by using NMR analysis.In addition, TOF-SIMS etc. can be used for analyzing when electrochromic layer is solid.
The purposes of EC element
It can be used for optical filter, lens unit, picture pick-up device or window member etc. according to the EC element 1 of the present embodiment.
Optical filter
There is EC element 1 according to the optical filter of the present embodiment and be connected to the active component of EC element 1.Active component For driving EC element and adjusting passes through the active component of the amount of the light of EC element.Active component for example can for transistor or MIM element.Transistor can have such as InGaZnO oxide semiconductor in active region.
Optical filter has the EC element 1 according to the present embodiment and is connected to the driving device of EC element 1.Fig. 2 is to show The schematic diagram of one example of the EC element 1 of driving device 20 and driven device 20 driving of EC element 1.The present embodiment EC element 1 driving device 20 have driving power 8, resistance selection device (selector) 9 and controller 7.
Driving power 8 is applied to the EC material in EC layer 12 included to EC element 1 and electricity required for electrochemical reaction occurs Pressure.Driving voltage is more preferably constant voltage.This is because absorption spectrum can be due to the material when EC material is made of multiple material The difference of the oxidation-reduction potential of material and the difference of absorptivity and change, therefore constant voltage is preferred.From driving power 8 Voltage applies beginning or applies state to be kept by from the signal of controller 7, and is wherein controlling EC element 1 The application state of voltage is kept constant during light transmittance.
Resistance selection device 9 in the closed circuit for including driving power 8 and EC element 11 (not shown) of convert resistance device and Big 2 (not shown) of resistor of resistance ratio resistor 1, and selected resistor is connected in series.The resistance of resistor R1 Preferably at least it is less than the maximum impedance of element closed circuit, preferably 10 Ω or less.The resistance of resistor R2 is preferably greater than member The maximum impedance of part closed circuit, preferably 1M Ω or less.Note that resistor R2 can be air.In this case, although closing Closing on circuit stricti jurise to be open circuit, but can think that circuit is closed circuit and regarding air as resistor R2.
Controller 7 sends switching signal to resistance selection device 9 with the switching of control resistor R1 and resistor R2.
Lens unit
Lens unit according to the present embodiment includes having the imaging optical system of multiple lens and with EC element 1 Optical filter.Optical filter can be set between multiple lens or the outside of lens.Optical filter is preferably provided at the light of lens On axis.
Picture pick-up device
There is optical filter according to the picture pick-up device of the present embodiment and receive the light receiving element of the light through optical filter. Specifically, picture pick-up device can be camera, video camera or mobile phone with camera etc..It can be so that having light Form that the main body of receiving element and lens unit with lens can be separated from each other forms picture pick-up device.When imaging When main body and lens unit can be separated from each other in equipment, the invention also includes wherein when being captured used as with take the photograph As the form of the not androgynous optical filter of equipment.Note that in such cases, the allocation position of optical filter can be lens unit Outside, between lens unit and light receiving element or between multiple lens (when lens unit has multiple lens) etc..
Fig. 3 A and Fig. 3 B are an example for showing the composition of the picture pick-up device 100 using the optical filter of the present embodiment Schematic diagram.
Picture pick-up device 100 is the picture pick-up device with lens unit 102 and camera unit 103.Lens unit 102 has Optical filter 101 and imaging optical system with multiple lens or lens group.Optical filter 101 is the filter of above-mentioned the present embodiment Light device.
For example, in figure 3 a, lens unit 102 is indicated through its rear focus type being focused on rear side of aperture Zoom lens.Four lens groups are arranged in the following order from object side: the first lens group 104 with positive refracting power has negative Second lens group 105 of refracting power, the 4th lens group 107 of the third lens group 106 and positive refracting power with positive refracting power. Change the distance between the second lens group 105 and the third lens group 106 and comes zoom, and one of mobile 4th lens group 107 Divide to focus.
Lens unit 102 has aperture 108, He for example between the second lens group 105 and the third lens group 106 There is optical filter 101 between three lens groups 106 and the 4th lens group 107.It configures lens group 104~107, aperture 108 and filters Device 101 makes through the light of lens unit through each lens group 104~107, aperture 108 and optical filter 101, and can be into Exercise the adjusting of the light quantity with aperture 108 and optical filter 101.
Lens unit 102 is connected such that detachable relative to camera unit 103 via installation component (not shown).
Note that although the third lens group 106 of the configuration in lens unit 102 of optical filter 101 and the in the present embodiment Between four lens groups 107, but the configuration of picture pick-up device 100 is without being limited thereto.For example, optical filter 101 can be located at aperture 108 Last stage (pre-stage) (in object side) or rear stage (103 side of camera unit), or first to fourth can be located at thoroughly Any one last stage or rear stage of microscope group 104~107 or between lens group.Note that existing in the configuration of optical filter 101 In the case where the position that light is assembled, the advantage etc. that the area of optical filter 101 reduces is obtained.
In addition, the composition of lens unit 102 is not limited to above-mentioned composition and can properly select.For example, in addition to rear coke , can be using the interior focus type being focused by it in the aperture last stage except point-type, or other types can be used. Furthermore, it is possible to properly select other than zoom lens such as fish eye lens or the first-class special lens of Macro Lens.
Camera unit 103 has glass blocks (block) 109 and light receiving element 110.Glass blocks 109 is such as low-pass filtering The glass blocks such as device, panel or colour filter.In addition, light receiving element 110 is the sensor list for receiving the light by lens unit Member, and can be such as CCD or CMOS photographic device.In addition it is possible to use such as photodiode optical sensor, and And acquisition and output can be suitably used about those of luminous intensity or the information of wavelength.
As shown in Figure 3A, when optical filter 101 is embedded in lens unit 102, driving device can be only fitted to lens unit In 102 or it can be only fitted to outside lens unit 102.When configuration is when lens unit 102 is outer, driving device is viscous by wiring The EC element 1 in lens unit 102 is connected to drive control.
In addition, optical filter 101 configures in lens unit 102 in the composition of above-mentioned picture pick-up device 100.However, this Invention is not limited to the form and can be configured with any form, as long as optical filter 101 configures the conjunction in picture pick-up device 100 Suitable position and light receiving element 110 is configured to receive the light for passing through optical filter 101.
For example, as shown in Figure 3B, camera unit 103 can have optical filter 101.Fig. 3 B is to show the present embodiment The figure of the composition of another example of picture pick-up device, to have the composition of the picture pick-up device of optical filter in camera unit 103 Schematic diagram.In figure 3b, optical filter 101 for example configures the positive last stage in light receiving element 110.When optical filter 101 is built in When in picture pick-up device, since the lens unit 102 of connection is not needed with optical filter 101, thus it is configured to using existing Lens unit 102 tunable optical picture pick-up device.
The picture pick-up device 100 of the present embodiment is applicable to the combined system with fader and light receiving element Product.For example, picture pick-up device 100 can be used for camera, digital camera, video camera or digital camera and can also fit Product therein such as mobile phone or mobile phone, PC or tablet computer etc. are built in for picture pick-up device.
According to the picture pick-up device 100 of the present embodiment, in the case where using optical filter 101 as light modulation component, light modulation Amount can be suitably changed by using single filter, and obtained package count and reduced and save space-efficient advantage.
Window member
There is EC element 1 according to the window member of the present embodiment and be connected to the active component of EC element 1.Active component For driving EC element and adjusting passes through the active component of the amount of the light of EC element.Active component can be for example, transistor or MIM element.Transistor can have such as InGaZnO oxide semiconductor in active region.
Fig. 4 A is the perspective view for showing the light-regulating window as window member for using the EC element 1 according to the present embodiment, and Fig. 4 B is the schematic diagram for showing the sectional view of the X-X' acquisition along Fig. 4 A.The light-regulating window 111 of the present embodiment includes EC element 1 (optical filter), the transparent panel 113 for clamping EC element 1 and around entirety and make whole integrated frame 112.EC element 1 has There is driving device (not shown), which can be integrated in frame 112 or can be only fitted to outside frame 112 simultaneously And EC element 1 is connected to by wiring.
The material of transparent panel 113 is not particularly limited, as long as it is with high transparency, and is worked as and is considered as Preferably glass material when window.Arbitrary material can be used for frame 112, and cover EC element 1 at least part and It is general that there is those of integrated form may be considered frame.Although EC element 1 is independently of transparent panel 113 in Fig. 4 B Component, but the transparent substrate 10 of such as EC element 1 may be considered transparent panel 113.
Such light-regulating window is suitable for for example adjusting the purposes of the amount of incident of the sunlight entered the room daytime.Due to light-regulating window Suitable for the adjusting of the heat other than the amount of sunlight, thus it can be used for controlling brightness or room temperature.In addition, light-regulating window Baffle (shutter) is suitable for for interdicting from outdoor to the indoor visual field.Such light-regulating window is suitable in addition to building The window of vehicle such as automobile, train, aircraft or ship other than windowpane.
As described above, the EC element 1 of the organic compound in EC layer 12 comprising being indicated by general formula (1) can be used for filtering Light device, lens unit, picture pick-up device or window member etc..Each optical filter, lens unit, picture pick-up device and window of the present embodiment Component only with the organic compound indicated by general formula (1) or with the organic compound indicated by general formula (1) and can have it The EC compound combination that the coloring of its wavelength band absorbs provides various absorption colors.Further, since each optical filtering of the present embodiment Device, lens unit, picture pick-up device and window member include the organic compound indicated by general formula (1), thus saturating under colour killing state The bright available improvement of property.
Embodiment
Although the present invention will be described in more detail by embodiment below, but the invention is not restricted to this.
Embodiment 1 (synthesis of example compound A-3)
Tetrahydrofuran (80ml) and diisopropylamine (16ml, 110mmol) are added in reactor, and by mixture It is cooled to -70 DEG C.After 1.6M n-buli hexane solution (70ml, 110mmol) is gradually dropped in solution, by temperature liter Up to 0 DEG C, prepare LDA solution.In addition, preparing N, nicamide (18g, 100mmol), tri-isopropylborate (25ml, 110mmol) and tetrahydrofuran (80ml), and mixture is cooled to -10 DEG C.By previously prepared LDA solution After being gradually dropped in solution and solution being stirred at room temperature 2 hours, [1,1 '-bis- (diphenylphosphinos) is added thereto Ferrocene] palladium chloride (II) chloride dichloromethane adduct (1.7g, 2mmol), 4- Bromoquinoline (13.7g, 66mmol), tetrahydro Furans (160ml), potassium phosphate (139g, 250mmol) and water (150ml), and solution is stirred 14 hours at 60 DEG C.It will Reaction solution is placed to room temperature, and diatomite filtering and the extraction with ethyl acetate are carried out.By the anhydrous sulphur of the product of extraction Sour sodium is dried and concentrated, and obtains brown solid.By its column purification (eluent: hexane/ethyl acetate=1/2), it is solid to obtain yellow Body intermediate 11 (16g, yield (yield): 80%).
Tetrahydrofuran (40ml) and diisopropylamine (8ml, 55mmol) are added in reactor, and mixture is cold But to -70 DEG C.After 1.6M n-buli hexane solution (35ml, 55mmol) is gradually dropped in solution, raise the temperature to 0 DEG C, prepare LDA solution.The tetrahydrofuran solution (40ml) of intermediate 11 (15g, 50mmol) is being gradually dropped it in solution Afterwards, room temperature is raised the temperature to, and solution is stirred 16 hours.In addition saturated ammonium chloride solution and solution is stirred It after 30 minutes, is sequentially washed with water and methanol by the crystal that filtering obtains, obtaining grey powder intermediate 12, (7.4g is received Rate: 64%).
Intermediate 12 (4.6g, 20mmol), n-butyl alcohol (70mL) and hydrazine monohydrate (10ml, 200mmol) are added to It is stirred 12 hours in reactor and at 100 DEG C.After cooling, water is added in the solution, is then concentrated, consolidate Body.By its column purification (eluent: ethyl acetate/methanol=10/1), obtain pale brownish solid Intermediate 13 (2.8g, yield: 64%).
It in the reactor by intermediate 13 (2.2g, 10mmol) and n,N-Dimethylformamide (15mL) addition, and will Mixture is cooled to 5 DEG C in ice bath.After potassium tert-butoxide (2.2g, 20mmol) is added in solution, by solution in phase Stirred 30 minutes at a temperature of, and will in n,N-Dimethylformamide (5mL) diluted iodomethane (3.1g, 22mmol) it is added dropwise in solution.After solution stirs 30 minutes at that same temperature, cooling bath is removed, by solution in room temperature Lower stirring 3 hours.Saturated sodium bicarbonate water is added in reaction solution, is extracted with ethyl acetate, organic phase is mixed, it will Mixture is sequentially washed with water and saturated brine, and by the drying of mixture anhydrous sodium sulfate and is concentrated, and is obtained black-yellow Color solid.By its column purification (eluent: ethyl acetate/methanol=10/1), obtaining beige solid intermediate 14, (150mg is received Rate: 3%).
Prepare intermediate 14 (98mg, 0.4mmol), 1- iodo heptane (203mg, 0.9mmol) and DMF in the reactor (10ml), and solution is being heated to reflux lower stirring 8 hours.After the completion of reaction, it filters out the crystal of precipitation and uses second Nitrile washing, obtains 223mg example compound A-3 (yield: 80%).
The structure of compound A-3 is confirmed by NMR measurement.1H NMR (DMSO-d6,500MHz), σ (ppm): 10.22 (s, 1H), 9.81 (s, 1H), 9.48 (d, 1H), 9.41 (d, 1H), 9.31 (d, 1H), 8.82 (d, 1H), 8.40 (t, 1H), 8.27 (t, 1H), 5.17 (t, 2H), 4.74 (t, 2H), 2.06 (m, 4H), 1.79 (s, 6H), 1.50-1.22 (m, 16H), 0.87 (m,6H)。
Embodiment 2 (synthesis of example compound A-2)
Example compound A-3 (210mg, 0.3mmol) is dissolved in water.500mg Potassium Hexafluorophosphate is added dropwise and is dissolved in it In solution, and solution is stirred at room temperature 3 hours.Filter out the crystal of precipitation and sequentially with isopropanol and diethyl Ether washing, obtains 212mg example compound A-2 (yield: 96%).
The structure of compound A-2 is confirmed by NMR measurement.1H NMR (DMSO-d6,500MHz), σ (ppm): 10.22 (s,1H),9.81(s,1H),9.48(d,1H),9.41(d,1H),9.31(d,1H),8.82 (d,1H),8.40(t,1H), 8.27(t,1H),5.17(t,2H),4.74(t,2H),2.06(m,4H),1.79(s, 6H),1.50-1.22(m,16H),0.87 (m,6H)。
Embodiment 3 (production of electric driven color-changing part and the evaluation of characteristic)
Perchloric acid tetrabutylammonium as electrolyte is dissolved in propylene carbonate with the concentration of 0.1M, then will be implemented The example compound A-2 of example 2 is dissolved with the concentration of 40.0mM, obtains EC medium.Next, there is transparent conductive film in a pair (ITO) end at four angles of glass substrate forms insulating layer (SiO2).For limiting the PET film of the distance between substrate (Teijin DuPont Films Japan Limited, Melinex (registered trademark) S, 125 μ m-thicks) configuration has in a pair Between the glass substrate of transparent electrode film.Then, other than the inlet for injecting EC medium, substrate and PET film pass through Epoxy bonding agent is bonded and seals.As described above, production has the empty room (cell) of inlet.Next, by above-mentioned side After the EC medium obtained in method is injected by vacuum impregnation, inlet is sealed by epoxy bonding agent, obtains EC member Part.
The EC element obtained at once after production shows 80% or so transmitance, thus has in entire visible-range There is high transparency.When the voltage of 2.0V is applied to the element, display is caused due to the reducing substances of example compound A-2 Absorption (λ max=490nm), and element colour.In addition, the application of -0.5V leads to colour killing.The element colored state with Can reversibly it change between colour killing state.Fig. 5 is the ultraviolet-visible absorption spectroscopy of the element made in the present embodiment.As Light source.Using from Ocean Optics, the DH-2000S deuterium halogen light source of Inc..
Embodiment 4 (synthesis of example compound A-42)
Prepare intermediate 12 (697mg, 3mmol) and THF (9mL) under nitrogen flowing in the reactor.Mixture is cooling To -5 DEG C, stirred 1 hour through 5 minutes or so dropwise addition methyl-magnesium-bromides (about, 1M, THF solution) (12ml), and by solution. After the reaction, 2M hydrochloric acid (5mL) is added dropwise, then adds 10M sodium hydroxide (5mL).By filtering and mistake under reduced pressure Sediment is filtered out, and is washed by ethyl acetate, water phase is further extracted with ethyl acetate twice.Organic phase is concentrated And column purification, to obtain intermediate 15 (534mg, the yield: 72%) as powder in the reactor.
Prepare intermediate 15 (99mg, 0.4mmol), 1- iodo heptane (452mg, 2.0mmol) and acetonitrile in the reactor Solution is being heated to reflux lower stirring 48 hours by (10ml).After the reaction, the crystal of precipitation is filtered, and passes through second Nitrile washing.In water by the dissolution of crystals of acquisition.Ammonium hexafluorophosphate (500mg) is added dropwise and is dissolved in solution therein, and will be molten Liquid is stirred at room temperature 3 hours.It filters the crystal being precipitated and is recrystallized with propyl alcohol/Di Iso Propyl Ether, to obtain 118mg Example compound A-42 (yield: 40%).
The structure of compound A-42 is confirmed by NMR measurement.
1H NMR(DMSO-d6,500MHz),σ(ppm):10.12(s,1H),9.66(s,1H),9.42 (m,2H),9.26 (d,1H),8.82(d,1H),8.42(t,1H),8.26(t,1H),5.22(m,2H),4.76 (t,2H),2.13(m,4H), 1.96(s,3H),1.50-1.21(m,16H),0.85(m,6H)。
Embodiment 5 (production of electric driven color-changing part and evaluating characteristics)
In embodiment 3, in addition to using example compound A-42 come other than replacing example compound A-2, by with implementation Example 3 identical method produces element.When the voltage of 2.0V to be applied to the element of the present embodiment, display is based on instantiating Close the absorption (λ max=501nm) of the reducing substances of object A-42.In addition, the voltage of application -0.5V, element colour killing, and show Reversible coloring and colour killing.
Embodiment 6 (synthesis of example compound A-45)
Prepare DMF (10mL) and sodium hydroxide (85mg, 2.1mmol) under nitrogen flowing in the reactor.By mixture It is cooled to after 0 DEG C, the DMF solution of intermediate 15 (420mg, 1.7mmol) is added dropwise.After stirring solution 30 minutes, delay EtI (ethyl iodide) (316mg, 2.0mmol) slowly is added dropwise, raises the temperature to room temperature, and solution is stirred 12 hours.? After reaction terminates, saturated brine solution is added, and extracted by ethyl acetate.Organic phase is concentrated and column is pure Change, to obtain intermediate 16 (360mg, yield: 77%) as powder in the reactor.
Prepare intermediate 16 (110mg, 0.4mmol), methylene chloride (5ml) and acetonitrile (5ml) in the reactor, in nitrogen Trimethyl oxygen tetrafluoroborate (473mg, 3.2mmol) is added under air-flow, and solution is stirred 12 hours.It is tied in reaction After beam, isopropyl ether is added, obtains crystal.In water by the dissolution of crystals of acquisition, it is molten that ammonium hexafluorophosphate (500mg) is added dropwise Solution is stirred at room temperature 3 hours in solution wherein, and by solution.Filter out the crystal of precipitation and with acetonitrile/diisopropyl Base ether recrystallization, to obtain 131mg example compound A-45 (yield: 55%).
The structure of compound A-45 is confirmed by NMR measurement.
1H NMR(DMSO-d6,500MHz),σ(ppm):10.07(s,1H),9.58(s,1H),9.44 (d,1H),9.38 (d,1H),9.27(d,1H),8.72(d,1H),8.45(m,1H),8.28(t,1H),4.78 (s,3H),4.51(s,3H), 3.51(q,4H),1.92(s,3H),1.06(t,3H)。
Embodiment 7 (production of electric driven color-changing part and evaluating characteristics)
In embodiment 3, in addition to use example compound A-45 replace example compound A-2 other than, by with embodiment 3 identical methods produce element.When the voltage of 2.0V to be applied to the element of the present embodiment, display is based on example compound The absorption (λ max=495nm) of the reducing substances of A-45.In addition, the voltage of application -0.5V, element colour killing, and show reversible Coloring and colour killing.
Embodiment 8 (synthesis of example compound A-41)
By intermediate 12 (241mg, 1.04mmol), methyl phenyl ethers anisole (1.2mL) and 3- mercaptopropionic acid (0.9 μ l, 0.01mmol) It is added in reactor.After mixture is cooled to 0 DEG C, it is added dropwise the concentrated sulfuric acid (0.6ml), and heated solution and 70 It is stirred 5 hours at DEG C.Sodium hydroxide solution is added in solution after cooling, so that reaction system becomes alkalinity.Water is added It adds in solution, extracts solution with chloroform, be then concentrated, to obtain solid.Make its column purification (eluent: oneself Alkane/chloroform), obtain intermediate 17 (310mg, the yield: 69%) as light yellow solid.
By intermediate 17 (270mg, 0.63mmol), 1- butyl iodide (1.15g, 6.3mmol) and 2-methyl cellosolve (1mL) is added in the reactor, and solution is stirred 24 hours at 100 DEG C.After cooling, ethyl acetate, filtering analysis are added It solid out and is further washed with ethyl acetate, obtains intermediate 18 (240mg, yield: 48%).
Intermediate 18 (240mg, 0.3mmol) is dissolved in water.Ammonium hexafluorophosphate (200mg) dissolution is added dropwise wherein Solution, and solution is stirred at room temperature 3 hours.It filters the crystal being precipitated and is sequentially washed with isopropanol and diethyl ether It washs, obtains 212mg example compound A-41 (yield: 85%).
The structure of compound A-41 is confirmed by NMR measurement.
1H NMR(CD3CN,500MHz),δ(ppm):9.31(s,1H),9.12(d,1H),9.08(d, 1H),8.98(s, 1H),8.97(d,1H),8.58(d,1H),8.39(t,1H),8.30(t,1H),7.25(d, 4H),6.93(d,4H),5.01 (t,2H),4.61(t,1H),3.80(s,6H),2.02(m,4H),1.37(m, 4H),0.96(t,3H),0.94(t,3H)。
Embodiment 9 (production of electric driven color-changing part and evaluating characteristics)
In embodiment 3, in addition to use example compound A-41 replace example compound A-2 other than, by with embodiment 3 identical methods produce element.When the voltage of 2.0V to be applied to the element of the present embodiment, display is based on example compound The absorption (λ max=505nm) of the reducing substances of A-41.In addition, the voltage of application -0.5V, element colour killing, and show reversible Coloring and colour killing.
According to the present invention it is possible to the light of the range near 500nm be absorbed by redox reaction to colour or colour killing And there is the organic compound of high stability to repeated oxidation reduction reaction.
Although the present invention has been described in reference example embodiment, it should be understood that the invention is not limited to disclosed Exemplary implementation scheme.The scope of the claims meets broadest explanation to cover all such improvement and equivalent knot Structure and function.

Claims (13)

1. a kind of organic compound, which is characterized in that it is indicated by following general formula (1):
In the general formula (1),
X1And X2Independently selected from by substituted or unsubstituted alkyl, substituted or unsubstituted aryl and substituted or unsubstituted virtue The group of alkyl composition,
R11~R18Independently selected from by hydrogen atom and substituent group at group, and by the R11~R18Each substituent group indicated For any one in following group: substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted Aryl, substituted or unsubstituted heterocycle, halogen atom and cyano,
R21And R22Independently selected from by hydrogen atom and substituent group at group, and by the R21With the R22What is indicated respectively takes Any one in Dai Jiwei or less group: substituted or unsubstituted alkyl, substituted or unsubstituted aryl and replace or do not take The aralkyl in generation, and
A1 -And A2 -Independently indicate monovalent anion.
2. organic compound according to claim 1, wherein the A1 -With the A2 -For identical anion.
3. a kind of electric driven color-changing part, characterized in that it comprises:
A pair of electrodes；With
The electrochromic layer between the pair of electrode is configured, the electrochromic layer includes according to claim 1 Organic compound.
4. electric driven color-changing part according to claim 3, wherein the electrochromic layer has and the organic compound The organic compound of different types of other types.
5. electric driven color-changing part according to claim 4, wherein the organic compound of other types is azophenlyene chemical combination Any one in object, metallocene compound and phenylenediamine compound and pyrazoline compounds.
6. electric driven color-changing part according to claim 3, wherein the electrochromic layer is with electrolyte and described to have The liquid of machine compound.
7. a kind of optical filter, characterized in that it comprises:
According to the described in any item electric driven color-changing parts of claim 3-6；With
It is connected to the active component of the electric driven color-changing part.
8. optical filter according to claim 7, wherein the active component is to drive the electric driven color-changing part and adjust The active component that section passes through the amount of the light of the electric driven color-changing part.
9. a kind of lens unit, characterized in that it comprises:
Optical filter according to claim 7；With
Imaging optical system with multiple lens.
10. a kind of picture pick-up device, characterized in that it comprises:
Imaging optical system with multiple lens；
Optical filter according to claim 7；With
Receive the photographic device of the light through the optical filter.
11. a kind of picture pick-up device, which is characterized in that the imaging optical system with multiple lens is removable from the picture pick-up device It unloads, the picture pick-up device includes:
Optical filter according to claim 7；With
Receive the photographic device of the light through the optical filter.
12. a kind of window member, characterized in that it comprises:
According to the described in any item electric driven color-changing parts of claim 3-6；With
It is connected to the active component of the electric driven color-changing part.
13. window member according to claim 12, wherein the active component be drive the electric driven color-changing part and Adjust the active component of the amount of the light by the electric driven color-changing part.
CN201910107431.0A 2018-02-06 2019-02-02 Organic compound and electric driven color-changing part Pending CN110117281A (en)

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US20160246152A1 (en) * 2015-02-20 2016-08-25 Canon Kabushiki Kaisha Organic compound, electrochromic element containing the same, optical filter, lens unit, imaging device, and window component
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US20160246152A1 (en) * 2015-02-20 2016-08-25 Canon Kabushiki Kaisha Organic compound, electrochromic element containing the same, optical filter, lens unit, imaging device, and window component
WO2017154681A1 (en) * 2016-03-10 2017-09-14 キヤノン株式会社 Organic compound, electrochromic element, electrochromic device, optical filter, imaging device, lens unit, and window material

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